WO1989007889A1 - Agent for imparting sustained-release properties to agricultural chemicals, sustained-release agricultural chemicals, and process for their preparation - Google Patents

Abstract

Composite particles comprising core particles of an agricultural chemical as an agriculturally active ingredient surrounded by an outer layer of fine hydrophobic particles are produced by depositing, on the surface of particles of a solid particulate agriculturally active ingredient, i.e., a compound with agricultural activity, fine particles of a hydrophobic substance having an average particle size of at most 1/5 of that of said agriculturally active ingredient in a predetermined weight ratio of the active ingredient to the hydrophobic substance, or anchoring the hydrophobic substance into the surface of the particles of the active ingredient to thereby fix the hydrophobic substance. In addition, the individual particles of the hydrophobic substance deposited or fixed on the surface of the agriculturally active ingredient as described above may be bound to each other by impact force and/or frictional heat to form a continuous covering film, thus giving composite particles of the agriculturally active ingredient comprising core particles of the active ingredient surrounded by the covering film of the hydrophobic substance. These composite particles can gradually release the active ingredient constituting the core particles through the surrounding layer of the hydrophobic substance at a controlled rate into water, thus showing sustained-release properties of the agriculturally active ingredient. Therefore, the composite particles are useful as an agricultural chemical having advantageous sustained-release properties and showing persistent biological effects. The composite particles can be made into an agricultural composition adapted for various preparations by mixing with various conventional adjuvants.

Description

 Details

 Paste Sustained-release imparting agent for pesticides, sustained-release pesticides and their manufacturing technology

 The present invention relates to a pesticide or a pesticide formulation containing a solid particulate pesticidal active ingredient, a sustained release imparting agent for imparting sustained release to the pesticidal active ingredient, and treated with the sustained release imparting agent. The present invention relates to a new sustained-release pesticide containing an active pesticide, and to a method of producing solid particles of an active pesticide having a sustained release. More specifically, the present invention relates to a technique for controlling the release of a pesticidal active ingredient by covering the particle surface of the solid pesticidal active ingredient with a fine powder of a hydrophobic substance.

 Background technology

Hitherto, many attempts have been made to impart sustained-release properties to various solid or liquid pesticidal active ingredients. Conventional methods for preparing sustained-release pesticides can be broadly classified into the following ^: 1) Encapsulation of the pesticide active ingredient ^ ^: 'in microcapsules (JP-A-58-144304, JP-A-59-20209) JP-A-58-21602, JP-A-59-53401, and (3) a method of converting an active pesticide into a clathrate compound with cyclodextrin (see JP-A-58-21602). Method of coating the granular nuclei granulated together with the solid component active ingredient alone or with an extender in agricultural chemicals such as powders and powders with wax or various resins (See Japanese Patent Application Laid-Open Nos. 57-126402 and 60-202801). However, up to this point, the dissolution and release of the pesticidal active ingredient have been achieved by applying a fine powder of a hydrophobic substance to the surface of the solid particulate pesticidal active ingredient and coating the surface. No attempt has been made to control and improve.

Solid agricultural chemicals such as granules and powders, when sprayed, come into contact with water, and the active ingredient contained in the formulation rapidly elutes from the formulation at a concentration higher than the concentration required for exerting biological effects. In some cases. In such a case, the active ingredients of pesticides that cause phytotoxicity to crops such as leaf blight or growth inhibition, or once eluted, are quickly decomposed and lost in water or soil, or lost by photolysis. May do so. As a result, the duration of the biological effect of the active ingredient is shortened. Therefore, if the pesticide active ingredient can be released from the pesticide formulation gradually and for a long period of time by the minimum amount of the pesticidal component necessary for controlling, such problems can be solved. Further, when the sustained-release property is imparted to the pesticide, it is not necessary to apply the pesticide over and over again, which is extremely economical and helps to prevent environmental pollution. However, each of the above-mentioned known sustained-release pesticides has advantages and disadvantages in solving such a problem. In other words, depending on the type of pesticide compound, it is impossible to enclose it in a microphone-mouth capsule or to form an inclusion compound with cyclodextrin. Some pesticide compounds cannot be processed as sustained-release preparations. Even if the conventional method for preparing a sustained-release formulation can be applied, satisfactory sustained-release properties cannot be obtained, or the obtained pesticide formulation has an insufficient control effect. In many cases, one of the objectives, such as holding and extending biological efficacy and reducing phytotoxicity, cannot be sufficiently achieved. In addition, there are still many technical and economical issues that need to be resolved because the technology for producing sustained-release pesticides is complicated and the raw materials used are expensive. . Therefore, as described above, the conventional techniques for producing sustained-release pesticides are still insufficient, and the development of new techniques is desired.

 In view of such circumstances, the present inventors have focused on a technique for modifying or improving the particle surface structure of a solid particulate pesticidal active ingredient, and imparting a desired sustained-release property to a solid particulate pesticide. Research was conducted to provide a new sustained-release imparting agent, a sustained-release pesticide obtained using the same, and a method for producing the same.

 Opening up the invention

The present inventors have found that the problems _c result that to the intensive study to solve the, the particle surface of the solid particulate pesticide active ingredient, Ni intends Motsuyo also high hydrophobicity original properties by re possessed by the particle surface It has been found that modification can impart favorable sustained-release properties to the pesticidal active ingredient particles. More specifically, the particles of the pesticidal active ingredient in the form of solid particles The entire surface is covered with the outer layer made of a fine powder of a hydrophobic substance adhered or immobilized on the surface, having an average particle diameter of one-fifth or less of the average particle diameter of the pesticidal active ingredient, or the adhesion described above. Or, if the particles of the immobilized hydrophobic substance fine particles are uniformly coated with a continuous film (coat-film) formed by coalescing the particles, the pesticide solid components in the form of solid particles become the central core. And a composite particle (compo site particles) of the pesticidally active ingredient having an outer envelope consisting of a hydrophobic substance fine powder or a coalesced coating of particles thereof was found to be produced. . Moreover, at this time, if the total amount of the hydrophobic substance fine powder is adjusted so as to be in the range of 0.05 to 1 part by weight of the hydrophobic substance per 1 part by weight of the pesticidal active ingredient, When the composite particles are placed in water, the pesticidal active ingredient can gradually elute from the core of the composite particles through the envelope layer of the hydrophobic substance, that is, the obtained pesticide. The composite particles of the active ingredient were found to exhibit sustained release of the pesticidally active ingredient.

Further, the composite particles of the pesticidal active ingredient produced as described above are mixed with adjuvants and bulking agents in the same manner as ordinary pesticides, and are mixed with powders, granules, wettable powders, suspending agents, pastes and the like. The pesticide formulation thus produced exhibits a favorable sustained-release effect, and therefore, a long-lasting biological effect inherent to the pesticidal active ingredient. It was found that benefits such as phytotoxicity were significantly reduced. Therefore, a first gist of the present invention provides a sustained-release imparting agent for a pesticide containing a solid particulate pesticidal active ingredient, which is characterized by comprising a fine powder of a hydrophobic substance.

Further, according to a second aspect of the present invention, a hydrophobic substance having an average particle diameter of 1/5 or less of the average particle diameter of the pesticidal active ingredient is formed on the surface of the solid pesticidal active ingredient. The center core particles of the pesticidal active ingredient produced by attaching the fine powder, or by impregnating and immobilizing the fine particles of the hydrophobic substance into the particle surface of the pesticidal active ingredient. The above-mentioned hydrophobic substance fine powder is coated on the surface of the composite particles containing the pesticide active ingredient, which comprises the outer layer of the hydrophobic substance fine powder surrounding the core particle, or the solid pesticidal active ingredient. Attach or fix the fine particles of the hydrophobic substance into the surface of the particles of the pesticidal active ingredient and fix them.The individual particles of the adhered or fixed hydrophobic fine particles are further impacted with each other. And / or coalesced by frictional heat Then, the center core particle of the pesticidal active ingredient produced by coating the particle surface of the pesticidal active ingredient, and a continuous coating of a hydrophobic substance surrounding the core particle. A pesticide containing composite particles containing the pesticidal active ingredient consisting of a hydrophobe, and the total amount of hydrophobic substance fine powder used is in the range of 0.05 to 1 part by weight of the hydrophobic substance per part by weight of the pesticide active ingredient. And a sustained release pesticide characterized in that: The gist of the third aspect of the present invention is that a hydrophobic fine powder having an average particle diameter of 1/5 or less of the average particle diameter of the solid particulate agricultural chemical active ingredient is added to 1 part by weight of the agricultural chemical active ingredient. On the other hand, the total amount of the hydrophobic substance used is in the range of 0.05 to 1 part by weight, and the hydrophobic substance-based fine powder is attached to the surface of the solid particulate pesticidal active ingredient particles, or Consists of biting the particles of the aqueous substance fine powder into the surface of the particles of the pesticidal active ingredient and immobilizing them, or if further desired or appropriate, these adhered or immobilized hydrophobic substance fine powders The central core particles of the pesticidal active ingredient are characterized in that the individual particles of the body are coalesced by impact and Z or frictional heat, thereby covering the particle surface of the pesticidal active ingredient. And the outside of the hydrophobic fine powder surrounding this core particle Or it is 闋 hydrophobic substance the continuous coating with complex preparation of pesticides and possible sustained release of the agrochemical active ingredient Ri form der particles consisting of.

 BEST MODE FOR CARRYING OUT THE INVENTION

The hydrophobic substance forming the hydrophobic substance fine powder used in the present invention is not particularly limited as long as it has water repellency to water. When a drop of water is dropped on the upper surface of a single flat plate made by compression-molding hydrophobic substance fine powder and the hydrophobic substance is hydrophobic to the required degree, the dropped water drop Does not wet and spread on the surface of the plate, and retains the shape of a 1 偭 drop. At this time, where the free surface of the still water droplet contacts the flat surface of the hydrophobic substance, The angle between the liquid surface and the solid surface

Defined as "contact angle". The greater the contact angle, the greater the hydrophobicity of the hydrophobic material.

 In the present invention, the contact angle of a hydrophobic substance to water is measured by the following measurement method as a measure of the hydrophobicity of a water-repellent substance.

 A fine powder of a hydrophobic substance is compression-molded (200 kg / erf) with a tablet molding machine to prepare a tablet-shaped disk having a diameter of 8.5 mm and a weight of 1 O Orag. Next, ion-exchanged water 5 was dropped on the upper surface of the tablet with a micro syringe, and the contact angle between the water droplet and the tablet surface one minute after the drop was measured with a goniometer (G-1 type manufactured by Elma Optics Co., Ltd.). ).

 When the contact angle between the free surface of the water droplet and the surface of the hydrophobic material measured by the above-mentioned measurement method is 70 degrees or more and shows a certain degree of hydrophobicity, the hydrophobic material is very effective in the present invention.

 Examples of the hydrophobic substance that can be used in the present invention include the following. Of course, it is not limited to these.

 (1) Higher fatty acids

 For example, stearyl acid, palmitic acid, rauric acid, myristic acid and the like are included.

 (2) Higher fatty acid metal salt

Examples include aluminum stearate, magnesium stearate, calcium stearate, etc. I do.

 (3) Titanium oxide treated with metal salts of high fatty acid

 Examples include titanium oxide treated with aluminum laurate and titanium oxide treated with aluminum stearate.

 (4) Hydrophobic white carbon, that is, hydrophobic silica

 Examples include alkylsilylated silicas, especially silicon dioxide treated with dimethyldichlorosilane.

 (5) Hydrophobic synthetic polymer

 Examples include polystyrene, polyamide, silicone, and the like.

Commercially available hydrophobic substances can be used as they are, but if necessary, commercially available hydrophobic substances should be used to reduce the average particle diameter to one-fifth or less of the average particle diameter of the active agricultural chemical used. It is good to use the active substance after pulverizing it. The average particle size of the hydrophobic substance fine powder used in the present invention varies depending on the average particle size of the pesticidal harmful component, but it is necessary that the average particle size is one fifth or less of the particle size of the pesticide active ingredient. , Preferably less than one tenth. If it is larger than one-fifth, it is difficult to adhere or immobilize the hydrophobic fine powder uniformly to the particle surface of the active agricultural chemical component or to apply it as a continuous film of uniform thickness. Yes The function of imparting a sustained release property to hydrophobic substances cannot be fully exerted. Also, the core particles of the active agricultural chemical and the coarse particles surrounding the core particles It is desirable that the composite particles of the pesticidal active ingredient composed of the surrounding outer layer of the aqueous substance have an average particle diameter of 50 microns or less. If the composite particles have an average particle size of more than 50 micron, the desired biological effect of the pesticidal active ingredient will not be sufficiently exerted. As a guideline, the average particle size of the core solid particulate pesticidal active ingredient varies from 5 micron to 500 micron depending on the type and formulation of the active ingredient compound. , But is not limited to this. Further, the average particle size of the hydrophobic substance fine powder may be in the range of 0.01 micron to 100 micron, but is not limited thereto.

Further, the amount of the hydrophobic substance applied to the surface of the solid particulate pesticidal active ingredient depends on the average particle diameter of the pesticidal active ingredient and the average particle diameter of the hydrophobic substance fine powder. It is necessary to apply the hydrophobic substance in a ratio of 0.05 to 1 part by weight to 1 part by weight. Of course, the ratio of the amount of the pesticidal active ingredient to the amount of the hydrophobic substance may be appropriately changed within this range for the purpose of obtaining the optimum sustained release. However, if the amount of the water-repellent substance fine powder is less than 0.05 parts by weight, the pesticide active ingredient may be uniformly adhered or fixed to the entire particle surface, or may be applied as a uniform film. As a result, the effect of imparting sustained release cannot be sufficiently exerted. Conversely, if the amount is more than 1 part by weight, the hydrophobic substance fine powder is excessively applied around the pesticide active ingredient particles. In this case, the effect of imparting sustained release is exerted, but the natural biological effect of the pesticidal active ingredient is reduced, and therefore, it is not preferable to use an excessively large amount of fine water powder.

 The pesticidal active ingredient in the form of solid particles that can be used in the present invention is not particularly limited in kind, and any active ingredient compound used in ordinary pesticides or pesticide preparations can be used. Examples of the pesticidal active ingredient include, for example, the following pesticidal compounds, but are not limited thereto.

Examples of pesticides

 Pyridafentione, Chlorpyrifos-methyl, Chlorpyrifos, Bamidothion, Dimethate, Hosalon

PMP, DMTP, CVMP, dimethylvinphos, acephate, salicion, DEP, EPN, NAC, THC, MIPC, BPMC, PHC MPC XMC, etyofencalp, pirimicarb, bendiocalp, resmetrine , Rotenone, CPCBS, Kezoresen, Chlorbenzilate, Chloropropyl acetate Phenylisobromolate, Tetrazionate, Quinomethionate, Amitraz, Benzomate, Binapril, Hydroxyl trioxide Cyclohexyltin, phenylbutane oxide, polynactin complex, methylisothiosinate, meszolefenphos, molantel tartrate, benzepin, cartap, thiocyclam, mesomil, oxamil, butoxycarboxime, Difulvenslon, Buprof ジ ン Jin, etc.

 Examples of fungicides

 Copper sulfate, basic copper sulfate, basic copper chloride, cupric hydroxide, oxine copper, captan, zineb, maneb, manzeb, polycarbonate, provineb, ziram, thiuram, minoleneb, Captafol, dichlorofluanid, TPN, fusaride, phosmethyl torquo, thiophane-trimethyl, benomyl, thiaventazol, iplodione, vincolozolin, procymidone , Blastocydin S, Kasugamycin, Polyoxin, Paridamycin A, Streptomycin, Oxitetracycline, Novopiocin, Minorediomaisin, PCNB, Hydroxyisoxazol, Dazomecin , Chloroneb, triphenyltin hydroxide, MAF, MAFA, dithianon, phenazine oxide, CNA Dimethymol, anilazine, oxycaslevoxin, mepronisole, probenazole, isoprothiolane, metasulfocap, fluorimido, trifolin, triazimehon, tricyclazo — Le, josetil, guazatine, metalaxyl, etc. Examples of herbicides

CP, MCPP, MCPB, Phenothiol, Naproanilide, DNBP, Aikisinil, CNP, Chromate Xinole, Bienox, MCC, IPC, Fenme Fam , MBPMC, DCPA, § La crawl, Napuronoヽ⁰ mi de, Jifue cyanamide, professional Pizami de, Ashu lamb, DCMU, Li news outlet , Sidurone, dimuron, methyl dimuron, sorbitol, isoperon, simazine, atrazine, propazine, simetryn, ametrine, promethrin , Cyanadine, metribudine, tarbasil, bromacil, renacil, PAC, norflurazon, bentazon, oxosaziazon, pyrazolate, no-lacote, diquat, trifluralin, besrosin, nitratra Lin, Pendimethalin, MDBA, Vichloram, TCTP, TCA, Tetrabion, Amiprophosmethyl, SAP, Glyphosate, Hosamimmmonium, Bialaphos, Glufosinate, ACN, DBN, DCBN , Acephenonone, aroxydim, chlorthalim, tricropil, DSMA, sodium chlorate, sodium cyanate Tritium, sodium sulfamate, methyl 2-{[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] aminosulfonylmethyl} benzoate.3 , 7-Dichloro-8-quinolinecarboxylic acid, N- (1,1-dimethylbenzyl) -2-bromo-t-butylacetamide, 2- (1,3-benzothiazole-2-yloxy) ) -N-methylacetanilide, etc.

Examples of plant growth regulators

Ansimidol, indolebutyric acid, ethyclosate 2-chloro mouth ethylphosphonic acid, oxyethylene higher alcohol, oxyquinoline sulfate, chloroxyhonac, alkaline coat, dichloroprop, Dike black, 1-naphthyl acetate, nicotinic acid amide, phenol Acetic acid, benzylaminoinoprine, maleic hydrazide, mefluidide, etc.

 These pesticidal active ingredients can be used alone or in the form of a mixture of two or more. The common names of the above-mentioned compounds of the pesticidal active ingredient are given in "Agrochemical Handbook 1985 Edition" (published by the Japan Plant Protection Association, January 30, 1986).

 In carrying out the present invention, a method of adhering or immobilizing a hydrophobic substance fine powder in the form of a uniform outer layer on the entire surface of solid particulate pesticidal active ingredient particles, or coalescing hydrophobic substance particles The application method in the form of a coated film is not particularly limited, but may be, for example, the following method.

(1) A method in which a predetermined amount of an active ingredient of solid particulates and a fine powder of a hydrophobic substance are put into a centrifugal rotation type ball mill, and these substances are rotated together with the ball. In this centrifugal rotation ball mill method, the raw material is rotated together with the metal ball in the mill and collides with the inner wall of the mill and the ball, so that the raw material is uniformly mixed and the water-phobic material is removed. The fine powder is uniformly spread and adhered to the surface of the pesticidal active ingredient particles, and further, mechanical action of compression, shearing and impact is given to each particle. Attached to the particle surface. At the same time as, or after, this adhesion, the part of the particles of the pesticidal active ingredient is partially eaten into the surface layer and the root is brought down. Thus, it is fixed in this way. Further, as the above process further proceeds, the hydrophobic substance fine particles adhered and / or fixed to the particle surface of the pesticidal active ingredient are further subjected to shrinkage, shearing, impact action, frictional heat action, etc. As a result, the fine particles of the hydrophobic substances coalesce with each other to form a continuous film around the pesticide impeached component particles (core particles).

 (2) Disperse the pesticide active ingredient particles and fine particles of water in a predetermined amount in a high-speed airflow, and perform mechanical action mainly by impact force by collision, action of frictional heat by collision, and other external effects. A method of impact action in a high-speed air stream that gives energy to solid particles.

 In this method, too, because of the mechanical action of compression, shearing and impact and the action of frictional heat, the hydrophobic substance fine particles adhere to the surface of the pesticidal active ingredient particles or are fixed as described above. The process progresses until a continuous film is formed in which the hydrophobic fine particles are coalesced together. The equipment for implementing the method of applying an impact in this high-speed air stream includes a commercially available Hybridization System (Nara Machinery Co., Ltd.) There is a dry powder surface reformer manufactured by MFG. Co., Ltd.) and a commercial mechano-fusion system (trade name of surface fusion device manufactured by Hosokawa Miclon Co., Ltd.).

In carrying out these methods (1) and (2), heating and cooling may be performed as necessary. The formulation containing the sustained-release pesticide of the present invention is not particularly limited, and is, for example, powder, DL (driftless) powder, flow dust, wettable powder, fine granules: F, fine granules Preparations, granules, suspensions, hydrated granules, pastes, and the like, and the preparation of the preparation can also be carried out using a device generally used in the present invention. What is necessary is just to mix the obtained composite particles of the pesticidal active ingredient, the auxiliary agent and the extender, and to carry out by a usual means. The adjuvants used for producing the sustained-release pesticide of the present invention may be various adjuvants generally used for pesticide formulations. Examples of the auxiliary include anions such as alkyl sulfates, alkyl sulfonic acids, alkyl sulfonic acids, polyethylene glycol esters, polyethylene glycol esters, and polyhydric alcohol esters. Examples include surfactants, nonionic surfactants, various antioxidants, ultraviolet absorbers, hydrolysis inhibitors, and physical property improvers.

Further, extenders that can be used in the present invention are also those generally used in agricultural chemical formulations. Examples of the bulking agent include clay, kaolin, sericite, jiglite, tazolex, acid clay, calcium carbonate, magnesium carbonate, stone, diatomaceous earth, pumice, and zeolite. Minerals such as perlite, permeilite, attapulgite, bentonite, natural products such as starch and cellulose, xylol, methyl alcohol, ethyl alcohol, isopropyl alcohol, glycerin , Organic solvents such as water, propylene glycol, propylene glycol monomethyl ether, and methyl naphthalene; and water.

Example

 Hereinafter, examples will be given in order to specifically describe the present invention, but the present invention is not limited to only these examples. In the examples, “parts” means “parts by weight”.

Example 1 Dust

Kasugamycin powder (dullness 72.0%, average particle size 30 m) 4 parts of hydrophobic titanium oxide MT-100S (trade name of aluminum oxide phosphate-treated titanium oxide manufactured by Teikoku Chemical Co., Ltd., average particle One part is a centrifugal-rotation type ball mill (Okada Seie Co., Ltd., product of ball mill type mixer sold under the trade name Mechano Mill) with a diameter of 0.015it _m and a contact angle of 145 degrees with water drops. ), Set the temperature of the powder mixture to 50 ° C, and mix at 400 rpm for 30 minutes. In this way, complex particles of kasugamycin (a core particle of kasugamycin having an outer layer of hydrophobic titanium oxide applied thereto) were obtained. 0.35 parts of sugamycin complex particles (kasugamycin content 57.6%), 1.0 part of whitening force, 0.3 parts of isopropyl phosphid phosphate (a physical property improver) and 98.35 parts of clay The mixture was mixed with a mill to obtain a sustained-release powder containing 0.2% of kasugamycin.

Actual _Example 2 Fine granule F After mixing the kasugamycin complex particles (sugamycin content 57 ガ 6%) 0 5718 parts, polyvinyl alcohol 0.5 parts and clay 99.32 parts prepared in Example 1 with a hammer mill, the rolling granulator was used. Add 5 parts of water and granulate. After drying, the mixture was sieved and sized (65 to 250 mesh) to obtain a sustained-release fine granule F containing 0.1% of kasugamycin. Example 3 wettable powder

 2.1 parts of the kasugamycin complex particles prepared in Example 1, 5 parts of white carbon, 3 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate and 87.9 parts of fine powder mixed with a hammer mill As a result, a sustained-release wettable powder containing 1.2% of kasugamycin was obtained.

Example 4 suspension

 2.1 parts of the kasugamycin complex particles prepared in Example 1, 15.3 parts of fusalide (purity 98.5%), 2 parts of polyoxyethylene nonylphenyl ether, 10 parts of ethylene glycol, 0.2 parts of xanthan gum and 70.4 parts of water was stirred and mixed with a mixer to obtain a suspending agent containing 1.2% of kasugamycin and 15% of fusalide.

Example 5 ^ ¾

Validamycin A (purity 48.5%, average particle size 30 m) 4 parts of AEROSIL R-972 (trade name of dimethyl-capped silane-treated silicon dioxide manufactured by Nippon A. Lozir Co., Ltd., average particle 0.016 mm, water droplets A hydrophobic substance with a contact angle of 155 degrees) One part is the same centrifugal rotary ball mill as in Example 1. (Mechano mill) and the same operation as in Example 1 was performed to obtain composite particles of validamycin A having an outer layer in which aerosil R-972 was uniformly adhered and immobilized on the particle surface of validamycin A. Was.

 Validamycin A composite particles produced in this way

(Validamicin A content 38.8%) 0 78 parts, white carbon 1 part, isopropyl acid phosphate

0.3 parts and 97.92 parts of Clay were mixed with a hammer mill to obtain a sustained-release powder containing 3% validamycin A. Example 6 wettable powder

 Acephate (purity 98.5%, average particle size 30ίί Βΐ) 4 parts of hydrophobic titanium oxide MT-100T (trade name of aluminum stearate-treated titanium oxide manufactured by Teikoku Chemical Co., Ltd.) One part of a hydrophobic substance having a particle diameter of 0.015 ιη and a contact angle of 140 ° with water droplets) 1 part was placed in the same centrifugal rotation type ball mill (mechano mill) as in Example 1 and mixed for 120 minutes to obtain the surface of the acephate particles. Then, acephate composite particles having an outer layer to which hydrophobic titanium oxide MT-100T (hydrophobic substance fine powder) was uniformly adhered were obtained.

63.5 parts of the polyester complex particles (acetone content 78.8%), 5 parts of white carbon, 2 parts of polyoxyethylene nonylphenyl ether, 2 parts of calcium ligne sulfonate and 2 parts 27.5 parts of fine powder was mixed with a hammer mill to obtain a sustained-release wettable powder containing 50% of acetate. ' Example 7 m a.

 After mixing 6.4 parts of the composite particles of acephate x-mix prepared in Example 6, 1 part of polyvinyl alcohol and 92.6 parts of crepe with a hammer mill, 15 parts of water was added, kneaded, and extruded. After granulation with a granulator, drying, and sieving, the granules were sized (14 to 32 mesh) to obtain sustained-release granules containing 5% of acephate.

Example 8 granules

 4 parts of NAC (purity 99.0%, average particle size 7 tm) and 1 part of AEROSIL R-972 were placed in an equipment of the brand name Hybridization System, and AEROSIL R-972 was placed on the surface of the NAC particles. (Fine particles of a hydrophobic substance) were uniformly adhered to obtain MAC composite particles having an outer layer.

 2.6 parts of this NAC composite particle (NAC content: 79.2%), 1 part of white carbon, 0.3 parts of isopropyl acid phosphate and 96.1 parts of CLE are mixed with a hammer mill, and sustained release containing 2% of MAC A powdery substance was obtained.

Example 9

 Biff: ι: A mixture of 4 parts of Knox (purity 96.5%, average particle size 15 m) and 1 part of stearate (average particle size 3 m), trade name, Hybridization system equipment Then, the composite particles of Bif X Knox whose particle surface of Biffe Knox was coated with a film of stearic acid were obtained.

The bi-knox composite particles (including bi-knox) 6.5 parts, 5 parts of sodium ligninsulfonate, 20 parts of bentonite and 68.5 parts of Clay were mixed with a hammer mill, and then 12 parts of water with a rolling granulator. Add and granulate. After drying, the mixture was sieved and sized (14 to 32 mesh) to obtain sustained-release granules containing 5% bifenox.

Example 10 M

 0.78 parts of complex particles of validamycin A prepared in Example 5, 2.6 parts of composite particles of MAC prepared in Example 8, 1 part of white carbon, 0.3 parts of isopropyl acid phosphate 95.32 parts of oyster cream were mixed with a hammer mill to obtain a sustained-release powder containing 0.3% of noridamycin A and 2% of NAC.

The sustained-release pesticide of the present invention can be in the form of an insecticide, a bactericide, or a plant growth regulator depending on the kind of the contained pesticidal active ingredient, and is used in the foliage of plants, in soil, or in water. First, the active ingredient can be gradually released from the pesticide. As a result, it has excellent medicinal properties over a long period of time and can reduce phytotoxicity to crops as compared with pesticides that do not have sustained release. By appropriately selecting the amount of the hydrophobic fine powder and the conditions of its particle size, the elution rate of the active ingredient can be freely increased or decreased. Third, the sustained-release pesticide of the present invention can be easily formulated by mixing with adjuvants as in the preparation of general pesticide formulations. Fourth, the sustained release of the present invention Since agrochemicals can be produced by a dry process without using a solvent, they can be applied to many pesticide active ingredients and have wide applicability. Test examples will be given to prove the above-mentioned usefulness of the present invention.

Test Example 1 Dissolution test of active agricultural chemicals in water (Test for sustained release)

 500 ππβ of deionized water from ion exchange was placed in a 1 £ capacity flask. To the water, add the complex particles of the pesticidal active ingredient prepared according to Examples 1, 5, 6, 8, and 9 in an amount corresponding to an amount of the pesticidal active ingredient of 250 rag. Then, using a dissolution tester (NTR-VS6 manufactured by Toyama Sangyo Co., Ltd.), maintain the water temperature at 20 ° C and stir the contents of the flask at 200 rpm. Samples were collected from the flask at predetermined time intervals, the active ingredient concentration in water (PPm) was measured, and the dissolution rate (%) was calculated by the following equation.

 Concentration of active ingredient at the time of each measurement in water

 (¾) =

 ^ Dissolution rate, w_The active ingredient 250mg ^ S dissolved in 3 temples underwater theory According to this dissolution test, the following is confirmed. If sustained release is provided to the composite particles of the pesticidal active ingredient, the elution rate (%) of the active ingredient into water will be less than 100% at first, and over time. In both cases, it is recognized that the dissolution rate gradually increases.

The test results are shown in Table 1. According to this, it was found that the pesticide of the present invention had sustained release. Chapter ： Table I Using Hydrophobic Substances f

 Run Hydrophobic substance Hydrophobic substance Ά Leaching rate (%)

 Να 睐 Aqueous substance fine powder (hydrophobic substance

 Particle size contact angle

 C "m) Example of effective composition

 After 2 r 麵 3B チ タ ン 24 titanium oxide MT- 1 OOS 0.015 145 0.05 1 mosquitoes, su, gamycin 35 42 S 52

 2 Titanium oxide MT-10 OS 0.015 145 0.1 1 Kasugamy, Non 30 38 4A

3 Titanium oxide MT-100 S 0.015 145 0.25 1 Kasugamai, Song 27 35

 4 Titanium oxide MT—10 OS 0.015 145 0.5 1

 5 Titanium oxide MT—1 OOS 0.015 145 1.0 1 r

 6 Titanium oxide MT— 1 OOS 0.015 145 0.05 5 'bar' J J ^, ^^, J Λ q 14 17 9ΠU 2

7 Titanium oxide MT—1 OOS 0.015 145 0.25 5 j, <, ϊ ノ) ^ *, a: A Ru 10 19

 u 1

8 Titanium oxide MT—10 OS 0.015 145 0.5 5 j <11 My: V A K B i inll 19

 xu 1

9 Titanium oxide MT—100 s 0.015 145 1.0 5 V V-mycin A 3 5 7 in u 1

0 Titanium oxide MT— i o o s 0,015 145 0.05 8 MAC 32 3 Titanium oxide MT— 1 OOS 0.015 145 0.Z5 • 8 28 i Jl 3

12 Titanium oxide MT—10 OS 0.015 145 0.5 8 N AC m u 25 oOn nn

 JU 3 13 Titanium oxide MT—1 OOS 0.015 145 1.0 8 10

 XQ22 91

 J 2 14 Titanium oxide MT—10 OT 0.015 140 0.05 E V no 4 t * no * A J¾ 43 AO

HO 36 5 15 Titanium oxide MT— 10 OT 0.015 140 1.0 6 Ano “No *” Ί J1l 40 AA 5 16 Titanium oxide MT—10 OT 0.015 140 0.25 E Case Z7 38 43 45 4 17 Titanium oxide MT—L 0 OT 0.015 0.5 E Acephate 24 35 40 41 4 18 Titanium MT—: L 0 OT 0.015 140 1.0 6 Acephate 19 30 34 36 4 19 Titanium oxide MT—: I 0 OT 0.015 140 0.05 1 Kasugamycin 31 34'39 46 5 20 Titanium oxide MT—: I 0 OT 0.015 140 0.25 1 Kasugamycin 26 30 35 41 4 21 Titanium oxide MT—: 0 OT 0.015 140 0.5 1 Kasugamycin 23 27 32 38 4

、 し tijt_ Use of aqueous material

 Run rn.J .Ww Aqueous matter soluble rate (%)

 Amount (spike aqueous substance

 Να Contact angle of hydrophobic fine particles

 (am) Example Active ingredient 2 o'clock (go ratio)

 22 Titanium oxide ΜΤ— 100Τ 0.015 140 1.0 1 Kasugamycin 18 21 27 32 3

23 Titanium oxide ΜΤ— 100Τ 0.015 140 0.05 9 Bifenox 18 19 22 25 3

24 Titanium oxide Τ 100 Τ 0.015 140 0.25 9 Biphenyl 15 18 .20 22 2

25 Titanium 酸 —100Τ 0.015 140 0.5 9 Bifenox 10 13 .15 17 2

26 Titanium oxide ΜΤ— 100Τ 0.015 140 1.0 9 Bifenox 9 10 11 12 1

27 Verodil R- 972 0.016 155 0.05 5 Validamycin A 7 9 10 13 1

28 Verodil R-972 0.016 155 0.1 5 Validamycin A 2 5 6 7

 29 Aerosil R-972 0.016 155 0.25 5 Validamycin A 1 3 3 4

 30 m / z Rodil R-972 0.016 155 0.5 S Validamycin A 1 2 3 4

 3 1 Aerosil R-972 0.016 155 1.0 5 Validamycin A 1 2 3 4

 32 Aerosil R-972 0.016 155 0.05 1 Kasugamishishi 11 13 15 18 2

33 Aerozil R-972 0.016 155 0.25 '1 Kasugamycin 6 9 10 14 2

34 Aerosil R-972 0.016 155 0.5 1 Sugamycin 5 8 9 12 1

35 Aerosil R-972 0.016 155 1.0 1 Kasugamycin 5 8 7 9 1

36 Aerosil R-g 72 0.016 155 0.05 8 NAC 29 41 51 53 5

37 Aerosil R-972 0.016 155 0.25 8 NAC 24 36 46 48 5

38 Verodil R-972 0.016 155 0.5 8 NAC 20 33 42 43 4

39 Verodil R-972 0.016 155 1.0 8 NAC 15 28 37 39 4

40 Stearic acid 3.0 90 0.05 9 Bifenox 36 41 44 47 5

4 i-story 8 * 3 0 on Q 1 q Bifenox 30 38 39

 42 Stearic acid 3.0 90 0.25 9 Bisenox 28 32 34 36 4

43 Stearic acid 3.0 90 0.5 S Bifenox 25 29 30 33 3

·

 Output rate (%) Hydrophobic substance Hydrophobic substance

Ru n, til ίΛ *

体 質の粒 の拔 3*角 Ι¾¾有効成分 ½例 有 効 成 分 1時 IH1後 2B¾FIU1¾ 3ϋ醒 5時 RJl後 Hydrophobic substance

3 * Angle of body grain Active ingredient ½Example Active ingredient 1 hour After IH1 2B¾FIU1¾ 3

 (β £) 1}; 1Β · ratio)

 No, Rix 20 23 24 28

 4 4 Steering 3.0 90 1.0 9 Vima

 Ama

 3.0 90 0.05 6 1 33 38 42 49

4 5 Stearic acid

 1 30 34 37 42

4 6 Stearic acid 3.0 90 0.25 6 * Γ _ai

4 7 stearate 3.0 90 0.5 6 A ^ ¹ off: Bok '2Β 32 35 39

4 8 Stearic acid 3,0 90 1.0 6 Asemate 27 30 31 35

4 9 Baltimic acid 5.0 85 0.05 1 No * No., Shin 36 39 42 47

5 0 Baltimic acid 5.0 85 0.1: 1 P 4 Mycin 31 35 36 42

5 1 Partimic acid 5.0 85 0.25 1 Pumycin 29 32 34 39

5 2 Noretimic acid 5.0 85 0.5 1 4 j zi, "V, no 26 30 31 36

5 3 Partimine 敌 5.0, 85 1.0 1 J 21 25 27 31

 》 Τ no no, no Λ 1 0 20 22 28

5 4 Lauric acid 5.0 90 0.05, 5 "

 18 22

5 5 ノ \ 15

 La phosphoric acid 5.0 90 0.1 5

 S A 1 9 14 17 19

5 6 lan ffi? 5.0 90 0.25 5 ba 1 Ϊ

 5 7 Lauric acid 5.0 90 0.5 5 / Λ 'J ytinno in 11 14 16

5 a Rauic acid 5.0 90 1.0 5 /, τ ΠΙ 7 8 9 12

 5 37 41 43

5 9 Myristic acid 1.0 75 0.05 8 N A G 3

6 0 Myristic acid 1.0 75 0.1 & 30 32 35 38

6 1 Myristic acid 1.0 75 0.25 8 N A C 27 29 31 35

6 2 Myristic acid 1.0 75 0.5 8 N A C 24 26 28 32

6 3 Myristic acid 1.0 75 1.0 8 N A C 20 Li. 23 25

 N 39 44 46 SO

6 4 Aluminum stearate 2.5 130 0.05 1

6 5 Aluminum stearate 2.5 130 0.1 1 Kasugamycin 35 39 42 45 •

Hoof | Articles «Use

 Knee water Hydrophobic substance Elution rate (%)

 Amount (睐 aqueous substance

 ΛΙϋ 1SH. ΊΖ »Mon / Agriculture active ingredient

 (¾) Real giant example Active ingredient 賴 After 2 o'clock 3 o'clock Note 5 o'clock separation of 24

 6 6 Aluminum stearate 2.5 130 0.25 1 Sumycin 35 ¾u

 6 7 Aluminum stearate 2.5 130 0.5 1 Kazugama, I, Non 33 35

 6 8 Aluminum stearate 2.5 130 1.0 1 Casca'isin 2 28 30 31

6 9 Aluminum stearate 2.5 130 0.05 9 Biphenol 2 28 34

7 0 Aluminum stearate 2.5 130 0.25 9 Bimanano,,, 22 22 27 •

7 1 Aluminum stearate 2.5 130 0.5 9 Hy'nofu cap 22

 7 2 Aluminum stearate 2.5 130 1.0 9 ** 7

 7 3 Magnesium stearate 4.0 120 0.05 5 A 30 J4

 7 4 Stearin ® magnesium 4.0 120 0.1 5

 7 5 Magnesium stearate 4.0 120 0.25 5, y <, no) * ^ ✓ ✓ 22

 7 6 Magnesium stearate 4.0 120 0.5 5, A <20

 7 7 Magnesium stearate 4.0 120 1.0 5 No, <

 7 8 Calcium stearate 1.0 140 0.05 8 A C 38 30

 7 9 Calcium stearate 1.0 140 0.1 8 3fl 32 '

 8 0 Calcium stearate 1.0 140 0.25 8 M A C 26 29 J

8 1 Calcium stearate 1.0 140 0.5 8 N A C 24 27

 8 2 Calcium stearate 1.0 140 1.0 8 N A C 20 22

 8 3 Polystyrene resin 5.0 115 0.05 6 Asphalt 39 45 49 54

8 4 Polystyrene resin 5.0 115 0.1 6 Assay 35 40 44 48

8 5 Polystyrene ta-fat 5.0 115 0.25 6 Asphalt 32 37 41 45

8 6 Polystyrene resin 5.0 115 0.5 6 Acetate 30 34 37 41

8 7 Polystyrene resin 5.0 115 1.0 6 Assay 25 29 32 36

—H. Use of hydrophobic substance

 Run JK Aqueous matter Aqueous matter amount (Hydrophilic matter solubility (%)

 Να hydrophobic substance 物 contact angle of particle size of fine powder / chy 槳 active ingredient

 ua_ ノ astounding example * Effective ingredient 1ΡΪΙΗ1 after 2:00 NOTE 3:00 After Itfl 5:00 赚 24:00 ffi ratio)

 108 Dani Titanium MT— 100T 0.015 140 0.03 1 Bifenox 82 86 94 100

 109 a σ-Jill R-972 0.016 155 0.03 D 2 Haridamycin A 74 80 86 94 10

 110 Verodil R-972 0.016 155 0.03 Kasugamycin .78 82 88 97 10

111 AEROSIL R—972 0.016 155 0.03, "NAC 84 92 100

 112 Stearic acid 3.0 90 0.03 Ratio 5 Bifenox 90 100

 113 Stearic acid 10.0 90 0.25 Asphalt 9Z 100

 \ ^ ノ

 114 Palmitic acid 5.0 85 0.03 Ratio 17 Kasugamycin 89 100

115 Palmitic acid 7.0 85 0.25 Kasugamycin 94 100

116 Lauric acid 8.0 90 0.Z5 Halidamicin A 92 100

 (Five)

 117 Aluminum stearate 8.0 130 0.25 Ratio 20 Kasugamycin 68 94 100

 (1)

 118 Magnesium stearate 8.0 120 0.25, 21 Noridamycin A 86 92 100

 119 Polystyrene t-resin 7.0 115 0.25 Acetate 82 90 100

 120 dani titanium 0.015 60 0.Z5 kasugamycin 100

 121 Titanium oxide 0.015 60 0.25, "Halidamycin A 100

122 Titanium oxide 0.015 60 0.25, 25 Asphalt 100

睐 Aqueous matter: Efficacy ffl Emission rate (¾)

 Hydrophobic substance Hydrophobic substance

 Ru n Jit (3¾ aqueous substance

 Hydrophobic, contact angle of particle size of substance fine powder ^ 5 Να / elimination active ingredient 輞 after 2 Ι 荬 ¾example active ingredient 2 hours after transversal 3 face 赚

123 Oxide titan 0.015 Ε0 0.25 Bifyunox 100

124 CaO 0.012 20 0.25 Casca'mycin 100

 1 ^ 28 NAC 100

 125 silicon dioxide 0.012 20 0.25

126 Methacrylic fat 0.4 65 0.25 Kasugamycin 100

127 Methacrylic resin 0.4 65 0.25 Asbestos100

Note 1) In Comparative Examples λ to ⁵ , the raw powder of the active ingredient compound was directly subjected to a dissolution test. one

Note ^{2), 6-30} No. Φ in parentheses under.銥to ^ Ding that the composite particles were prepared according to the method Wuyi施例numbered ⁰

Test example 2 Rice blast control effect test (Confirmation of sterilization efficacy)

 Rice (cultivar: Akihikari) seeds were soaked in water to germinate, and then seeded in a field prepared in a polyvinyl chloride greenhouse. Then, 28 kg after seeding, the rice seedlings at the 3 leaf stage were to be applied with the sustained-release powder containing the complex particles of kasugamycin prepared according to Example 1 so that the application amount was 3 kg Z 10 a. It was sprayed using a simple sprayer. Two days after spraying, rice blast fungus that had been sporulated in advance

 (Pyricu la ria oryzae): Cut the diseased leaves of approximately 3 cm square from the diseased leaves over the entire test plot and use them as an inoculum source to ensure that rice blast is always infected. It is now possible. Moisture was always present in the greenhouse. At 7 days after inoculation, the disease incidence rate (%) (relative to the total area of the rape) of rice blast on the rice leaf is investigated over time at intervals of 3 to 4 days after inoculation. Value (%) was calculated

 Percentage of diseased area in sprayed area, devalue (%)-(-) X 100

 This test was carried out in three sections of lnf in one section, and the average control value (%) was determined.

 Instead of the kasugamycin complex particles of Example 1, a non-sustained-release powder prepared using an untreated kasugamycin drug substance was used as a comparative drug.

The results are shown in Table 2. No .: 2 firewood

Run Hydrophobic substance Hydrophobic substance control m (%)

 Να Hydrophobic substance fine powder; ί ^ ίΡ

 ζ active 成分 active ingredient

 (Μ) Inoculation 7 days 铰

 Of: ffift ratio) 11 days after vaccination; day after vaccination 20 days after vaccination

1 Titanium oxide ΜΤ— 1 0 0 S 0.015 145 0,05 33 90 09 οϋ None

2 Titanium oxide M T— 100 S 0.015 145 0.25 unrii 90 59 None

3 Titanium oxide MT— 100 S 0.015 145 0.5 9 n4 j

 92 91 δ 62 None

4 Titanium oxide M T— 100 S 0.015 145 1.0 95 92 91 85 62 None

5 Verodil R— 9 7 2 0.016- 155 0.05 96 94, 91 82 63 None

6 Aerosil R— 9 7 2 0.016 155 0.25 9b 93 90 86 62

7 AEROSIL R--9 7 2 0.016 155 0.5 94 92 nr *

 90 85 62 None

8 Aerosil R—g 7 2 0.015 155 1.0 n i 92 90 85 62 None g Partimine 敌 5.0 85 0.05 SI 89 63 None

1 0 Partimic acid 5.0 85 0.25 n ifrb 93 90 83 60 None

1 1 palmitic acid 5.0 85 0.5 nc n j

 34 90 η η

 OD 59 None

1 2 Partimi ^ acid 5.0 85 1, 0 91 86 60 None

1 3 Aluminum stearate 2.5 130 0.05 nc n 92 n

 89 Β5 60 None

1 Aluminum stearate 2.5 130 0.25 95 92 89 85 62 None

1 5 Aluminum stearate 2.5 130 0.5 95 92 90 82 62 None

1 6 Aluminum stearate 2.5 130 1.0 94 91 90 81 62 None

1 7 Polyamide resin 5.0 125 0.05 96 94 90 62 59 None

1 8 Polyamide resin 5.0 125 0.25 96 93 89 85 60 None

1 9 Polyamide resin 5.0 125 0.5 95 93 90 85 60 None

2 0 Polyamide cell 5.0 125 1.0 95 93 90 84 60 None

Use of hydrophobic substance

 Hydrophobic substance Hydrophobic substance Kf excluding fifi (%)

 Amount (hydrophobic substance

 Hydrophobic substance fine powder Contact angle of particle size

Να intercept 萘 active ingredient

 (any m z After contact 11 days After transfer 14 days Fine 7 days After vaccination 20

 The Φ 7 days

 Bone

 2 1 Hibyo 剂 95 85 65 40 20 None

2 2 None ¾ cloth area 0 0 0 0 0

(13) (34) (58), (84) (35) Note) The number in parentheses in the isfiic cloth indicates the rate of the pathogenesis of the cloth.

Test example 3 Rice sheath blight control effect test (confirmation of the mirror endurance of bactericidal efficacy)

 A sustained-release powder containing validamycin A complex particles prepared according to Example 5 on rice (cultivar: Nipponbare 10 plants, 5-6 leaf stage) cultivated in a 9 cm diameter positive Was sprayed using a simple sprayer so that the application rate was S kgZlO a. Three days, seven days, and fifteen days after application, the bacterial culture of Rhizoctonia Solani (28 ° C), which was cultured for 7 days in a brass medium supplemented with 0.5% peptone (28 ° C), was used as the inoculum. The lg was inoculated into the strain of each pot. After inoculation, the rice was stored in a greenhouse for disease at 28-30 ° C and 90% humidity for 10 days. Then, the rice was taken out, and the rice leaf blight spot (mean value) (cm) of the rice leaf was measured. Protection) = (m

 This test was carried out in three discrepancies, and the average control value (%) was determined. In place of the complex particles of validamycin A in Example 5, untreated validamycin A bulk powder was used. A non-sustained release powder prepared in the same manner as in Example 5 was used as a comparative drug.

Table 3 shows the results. Table 3

Note) The values in parentheses in the non-spray plot indicate the average lesion length (cm) in the non-spray plot.

Test Example 4 Persistence test of insecticidal effect on potato aphid

 Table 4 shows the sustained-release wettable powder containing complex particles of acephate prepared according to Example 6 in potted cabbage (cultivar: mid-early, 10 to 11 leaf stage). The solution obtained by diluting in a predetermined multiple of the volume of water thus obtained was sprayed on a turntable from a spray gun so as to give an application rate of 150 β / a. After that, it is placed in a glass room, and after a predetermined number of days, the cabbage leaf is cut with a leaf punch having a diameter of 8 cm, and the leaf section is put into a plastic petri dish having a diameter of 9 cm together with adult peach aphids. After standing at a temperature of 25 ° C. for 48 hours, the mortality (%) was determined.

 This test was performed in triplicate to determine the average mortality (%). In Example 6, the untreated acephate bulk material was used instead of the acephate composite particles of Example 6. A non-sustained release wettable powder formulated in the same manner as above was tested as a comparative drug.

The results are shown in Table 4.

Section 4 Table

Use of sexual substances

 Hydrophobic substance hydrophobic substance ϋ: (hydrophobic substance

 Bu n dilution factor Chemical damage Hydrophobic ^ Particle size of fine powder Contact angle! / Chlorine active ingredient

 Να «ni) m (times) Direct 钕 7 days after U 21 days after B 28 days after

 Published by Shigeo)

 25 2000 100 None

2 0 Polystyrene resin 5.0 115 0.

 0.25 4000 100 None 2 1 Polystyrene ^ I Fat 5,0 115

1000 100 None

2 2 Specific mosquito agent

 2000 100 100 70

83 43 なし 2 4 比蛟薬剤 4000 100

83 43 None 2 4

2 5 No release zone

4Ο 0 no:-ο ο 35 ο jgL5 Persistence of insecticidal effect on Himetobin power 1C composite particles prepared according to Example 8 on rice (cultivar: Nipponbare, 1 plant, 4 leaf stage) grown in pots with a diameter of 11 cm Sustained-release powder containing, was sprayed by Midget Duster so that the application rate was 3 kg, 10 a. After that, the rice was placed in a glass room, and after a predetermined number of days, the rice body was covered with a polyvinyl chloride cylinder having a diameter of ll cm and a height of 30 cm, to which 10 female adult females of Himebin-bika were released. 24 hours after release, the number of live and dead insects was examined, and the insecticidal rate (%) was determined.

 This test was performed in triplicate, and the average mortality (%) was determined. Note that, in place of the NAC composite particles of Example 8, the untreated NAC drug substance was used instead of Example 8. A non-sustained-release powder formulation similarly prepared was used as a comparative drug.

Table 5 shows the results.

Hydrophobic substance. Insect rate (%)

 Ru n one jJcr 1¾ »hydrophobic

 <Contact angle 贵 (particle size of 物 ® 水性 水性

 Na (βΕ) / chy 槳 active ingredient 3 days after gangrene 抉 14 days after 7 days

 Fli view ^)

 1 Titanium enamel MT100—S 0.015 145 0.05 100 100 97 47 None

2 Titanium oxide MT 10 O-S 0.015 145 0.25 100 100 97 47 None

 •

3 Titanium oxide MT 100-S 0.015 145 0.5 ■ ibo 100 93 so None

4 Titanium coated MT 100-S 0.015 145 1.0 100 100 97 50 None

5 Verodil R-972 0.016 155 '0.25 100 100 37 47 None

6 Myristic acid 1.0 75 0.25 100 100 97

7 Calcium stearate 1.0 140 '0.25 100 iob 93 47 None

8 m 100 83 40 10 None

 0 0

9 None ¾¾ϋ 0 0

Ward

Test Example 6 Herbicidal effect and phytotoxicity test

A pot with a size of 1/5000 are filled with paddy soil (alluvial loam) and a chemical fertilizer (nitrogen: phosphoric acid: kali = 17:17:17) is applied as a base fertilizer. Fertilizer was applied 3 _g, and the pot was filled with water to make it flooded.

 ① Chemical damage test

 Three rice plants (variety: Nipponbare) at the 2 leaf stage were transplanted per pot, and on the third day after transplantation, sustained-release containing biphenox complex particles prepared according to Example 9 The granules were sprayed at a rate of 3 kg per 10 liters for herbicidal treatment, and the pot was filled with water to a depth of 5 cm. In the survey, the length of the browning part of the leaf where the browning part was clearly observed at the third leaf position of rice on the 21st day after the chemical treatment was measured as the browning part length (mean value) (cm).

 This test was carried out in a three-unit system, and the average value of the length of the browned portion (cm) was determined.

 The non-sustained-release granules prepared in the same manner as in Example 9 using the bifenox drug substance instead of the bifenox composite particles in Example 9 were used as comparative drug 1 And

 The results are shown in Table 6.

 ② Herbicidal effect test

The same sustained-release granules as above were added to another 15,000 scaled pot that had been submerged in water and 3 kg per 10 ares. Herbicidal treatment was carried out by granulating at the application ratio. After 10, 20, 30, 40, and 50 days after the treatment, seeds of germinated seeds of the rice breeder were seeded at 20 pots per pot, and the pots were filled with water to adjust the flooding depth to 3 cm. In the survey, the dry matter (g) of this weed was measured 24 days after each sowing day, and the weeding rate (%) was determined by the following formula. Weeding rate _(%) =-Nubies) X 100 Dry matter of Tainubie in the treatment area This test was carried out in triplicate to determine the average weeding rate (%). The results are shown in Table 6.

Section G Table

 Hydrophobic material Knee aqueous material naked τκ food 用 ε 'phytotoxicity (褀 change) Herbicidal rate (%)

Run substance

 Hydrophobics Fine powder Particle size Contact angle & (hydrophobic

 Να

 Cum) (Hit ratio of (¾)) Contrast with Jiao Ji agent 10 days after touch 20 days after 30 days after 40 days after gourd 50 days after

1 Titanium oxide MT—10 OT 0.015 140 0.05 15 100 100 100 90 78

2 Titanium oxide ΜΤ— 1 ΟΟΤ 0.015 140 0.25 14 100 100 100 88 79

3 Titanium oxide ΜΤ—100Τ 0.015 140 0.5 15 100.100 100 88 80

4 Titanium oxide MT— 100T 0.015 140 l.O 16 100 100 100 90 77

5 Silicone tij fat 2.0 150 0.05 18 100 100 100.89 78

6 Silicone resin 2.0 150 0.25 18 100 100 100 90 78

7 Silicone resin 2.0 150 0.5 17 100 inn 100 on nn

8 Silicon 3-fat 2.0 150 l.O 15 inn inn 100 o αoα 70

 0

9 Stearic acid 3.0 90 0.25 "16 100 1DD 100 88 77

10 Aluminum stearate 2.5 130 0.25 18 100 100 100 90 78

11 i mi-― ■ ― 100 100. 100 100 70 48

 (Invitation length 9.0c)

 12 85 100 100 98 75 52

13 87 100 100 97 73 50

14 No ward 0 0 0 0

 (0.21) (0.21) (0.20) (0.21)

 Note 2) Comparative ^ Agent 2 (Invention of Tokuyo Sho 57-126402 ^^)

 The polyethylene resin and polyethylene ^ tree JJg 樹 were sprayed and dried on the granules of the Chinese herb preparation 1 to obtain biphenox granules containing 1% by weight of polyethylene resin and polyethylene ft® ^ composite (Ifctit53: 47). ,

 Note 3) Ratio 剤 ^ 3 (from Japanese Patent Publication No. 60-202801)

 The granules of Comparative Pharmaceutical Agent 1 were coated with an emulsion containing wax and an acrylic resin to obtain Bibuenox granules treated with 23 L% of wax and acrylic resin (J £ ftifc6: 1).

α INDUSTRIAL APPLICABILITY As described above, according to the present invention, a pesticidal active ingredient can be eluted gradually and continuously for a long period of time. It is possible to provide a pesticide having sustained release which is useful in that it can be used.

Claims

The scope of the claims  1. A sustained-release imparting agent for agrochemicals containing solid particulate agrochemical active ingredients, comprising a fine powder of a hydrophobic substance.  ' Five 2. A fine powder of a hydrophobic substance having an average particle size of one-fifth or less of the average particle size of the pesticidal active ingredient is attached to the surface of the solid pesticidal active ingredient, or Manufactured by fixing and immobilizing fine particles of hydrophobic substance in the particle surface 10 Composite or solid particulate pesticides containing the active pesticide, consisting of the central core of the active pesticide and an outer layer of a hydrophobic fine powder surrounding the core The hydrophobic substance fine powder is attached to the particle surface of the active ingredient, or the hydrophobic substance fine powder is 15 The particles of the powder are bitten and immobilized, and the individual particles of the adhered or immobilized hydrophobic fine powder are coalesced together by impact force and / or frictional heat. The center core particle of the pesticidal active ingredient, which was produced by coating the particle surface of the pesticidal active ingredient, 20 An agricultural chemical containing composite particles containing an active agricultural chemical comprising a continuous coating of a hydrophobic material surrounding a core particle, and the total amount of hydrophobic fine particles used is 1 of the active agricultural chemical. A sustained-release pesticide characterized in that the ratio of hydrophobic substance per part by weight is 0.05 to 1 part by weight. 25 3. Fine powders of hydrophobic substances include stearic acid, palmitic Acid, Lauric acid, Myristic acid, Aluminum stearate, Magnesium stearate, Calcium stearate, Aluminum stearate Titanium oxide, Stearin 3. The sustained-release pesticide according to claim 2, wherein the pesticide is selected from aluminum oxide-treated titanium oxide, alkyl silylated silica, dimethyldichlorosilane-treated gay dioxide, polystyrene, polyamide, and silicone.  4. The sustained-release pesticide according to claim 2, further comprising an auxiliary and / or a bulking agent acceptable for the pesticide.  5. A hydrophobic fine powder having an average particle size of 1/5 or less of the average particle size of the solid pesticidal active ingredient is added to the total amount of the hydrophobic substance per 1 part by weight of the pesticidal active ingredient. Is used at a ratio of 0.05 to 1 part by weight, and a hydrophobic substance fine powder is adhered to the surface of solid particulate pesticidal active ingredient particles, or a hydrophobic substance is present on the surface of the pesticidal active ingredient particles. Consists of biting and immobilizing the particles of the guest fine powder, or, if desired or appropriate, impinges the individual particles of these adhered or immobilized hydrophobic guest fines together. The central core particle of the pesticidal active ingredient, which is characterized in that it is bonded by voice and / or frictional heat, thereby covering the particle surface of the pesticidal active ingredient, and surrounds the core particle. Hydrophobic substance Outer layer of fine powder or continuous coating of hydrophobic substance Ranaru preparation of pesticides and possible sustained release of the agrochemical active ingredient Ri form der of composite particles.